Quinolone Antibiotic Residues Research Articles

Label-free simultaneous detection of quinolone antibiotic residues using an origami paper–based electrochemical immunosensor

Label-free electrochemical sensors have gained popularity as point-of-care devices because they do not require complicated labeling procedures. However, they have difficulties detecting multiple analytes simultaneously. In this study, we developed a novel label-free electrochemical immunosensor on an origami paper–based analytical device (oPAD) for the simultaneous detection of quinolone antibiotics, in which norfloxacin (Nor) and enrofloxacin (Enr) were used as a model. The oPAD was designed with two antibody zones, each zone contains different antibodies. The oPAD has two thionine- and ferrocenecarboxylic acid-coated reagent zones, as redox species, which will generate the response current signals for the detection of quinolone antibiotics. The simultaneous current responses of thionine and ferrocenecarboxylic acid decreased proportionately when exposed to Nor and Enr concentrations, respectively. Under optimal conditions, this device provided linear range at concentrations of 0.01–10 µg/mL for the detection of Nor and Enr and limit of detection was calculated as 2.02 and 1.70 ng/mL, respectively. Moreover, this device demonstrates performance comparable to standard methods for the simultaneous detection of Nor and Enr in milk, honey, and fish. Therefore, label-free electrochemical immunosensors provide a highly potent, inexpensive, and portable method for detecting multiple quinolone antibiotics simultaneously on a single device.

Three-Dimensional Viologen-Based Lanthanide-Organic Frameworks: Photochromism and Fluorescence Detection of Quinolone Antibiotics.

Quinolone antibiotic residues, norfloxacin (NORF) and ciprofloxacin (CIP), have attracted more attention due to their frequent detection in surface water and food field, which seriously threaten the health of animals and humans. Rapid and efficient detection of NORF and CIP is critical for environmental testing and ecosystems. Herein, two novel isostructural viologen-functionalized Ln(III) complexes [Ln2L0.5(IPA)3]n (Ln = Eu, 1; Tb, 2; L = N,N'-bis (2-carboxyethyl)-4,4'-bipyridridylium dichloride, H2IPA = isophthalic acid) with a three-dimensional structure have been synthesized solvothermally. Complexes 1 and 2 exhibited reversible photochromism under UV light. In addition, complex 1 exhibits excellent pH tolerance and can be seen as an efficient fluorescent probe for the detection of NORF and CIP with detection limits of 7.90 × 10-7 and 9.48 × 10-7 M, respectively. Furthermore, the good photoresponsive and outstanding fluorescent properties of 1 were further exploited in dual-function paper involving erasable inkless printing and detection of NORF and CIP. Our work reports a new strategy for recognizing NORF and CIP based on the luminescent color change of the viologen-based Ln-MOFs, providing a new direction for the development of multifunctional materials.

Rapid detection and whole class control of quinolone antibiotics in pork based on surface‐enhanced Raman spectroscopy

AbstractThe problem of excessive quinolone antibiotic residues in pork has stimulated great attention from the international community. However, due to the diversity and structural similarity of quinolone antibiotics, it is difficult to perform multi‐residue rapid detection at the same time. Currently, antibiotic multi‐residue detection methods include ultra‐performance liquid chromatography (UPLC) and colloidal gold immunochromatography. However, it cannot be widely used in on‐site rapid detection due to its shortcomings such as the need for high cost and low sensitivity. Herein, we report the use of surface‐enhanced Raman spectroscopy (SERS) technology for the study of similar structures of quinolone antibiotics. A method for whole class control and rapid quantitative detection of all quinolone antibiotics in pork was established. By using the above method, the detection limit of single standard quinolone antibiotics was 10 μg L−1, and the detection limit of the mixed standard was 1 μg L−1, meeting the international requirements for the detection limit of quinolone antibiotics in pork. At last, by adding a variety of quinolone antibiotics to pork, the real detection set‐up was simulated. The recovery of standard addition was 86.6%–95.3%, and the whole class control method has been well applied, which is of great significance for the detection of pork quinolone antibiotics. Compared with colloidal gold immunochromatography, our method has 2.5 times the detection speed, 1/60 times the cost, and can be quantitatively detected. The method is simple, economical, and efficient and has great application value with broad application prospects in the field of rapid detection of pork antibiotics in the future.

Improved Sensitivity to Determine Antibiotic Residues in Chicken Meat by In-Line Solid-Phase Extraction Coupled to Capillary Electrophoresis-Tandem Mass Spectrometry.

Traditionally, capillary electrophoresis (CE) has been ruled out of many food safety applications, despite its inherent advantages, because its concentration sensitivity has been not high enough, mainly in relation to the monitoring of contaminants and residues, such as pesticides, veterinary medicines, environmental contaminants, toxins, etc. For this reason, researchers have proposed several strategies to overcome this limitation. So far, approaches based on chromatographic principles have been the most successful solutions. These approaches, known as in-line solid phase extraction, consist of the introduction of a small amount of stationary phase in the inlet section of the electrophoretic capillary (analyte concentrator, AC) to retain the analytes before separation takes place. In this chapter, this strategy is applied to CE coupled to tandem mass spectrometry (MS/MS) for the multiresidue detection of quinolone antibiotic residues in chicken meat. A previous sample treatment based on pressurized liquid extraction to obtain an optimum performance is also described.

In situ SERS detection of quinolone antibiotic residues in a water environment based on optofluidic in-fiber integrated Ag nanoparticles

In this paper, we present a microstructured optofluidic in-fiber Raman sensor for the detection of quinolone antibiotic residue in a water environment based on Ag surface-enhanced Raman scattering (SERS) substrate grown on the surface of the suspended core of micro-hollow optical fiber (MHF). Here, MHF has a special structure with a suspended core and a microchannel inside, which can become a natural in-fiber optofluidic device. Meanwhile, the self-assembled Ag SERS substrate can be grown on the suspended core's surface through chemical bonds, forming a microstructured optofluidic device with a Raman enhancement effect. Therefore, it can effectively detect the Raman signal of unlabeled trace quinolone antibiotic residue (ciprofloxacin and norfloxacin) inside the optical fiber. The results show that the ciprofloxacin and norfloxacin detection limits (LOD) are 10-10M and 10-11M, respectively. Compared with the maximum residue limit (3.01×10-7mol/L) stipulated by the European Union, the results are much lower, and an ideal quantitative relationship can be obtained within the detection range. Significantly, this study provides an in-fiber microstructured optofluidic Raman sensor for the label-free detection of quinolone antibiotic residue, which will have good development prospects in the field of antibiotic water pollution environmental detection.

Low concentration noroxin detection using terahertz spectroscopy combined with metamaterial.

The unreasonable use of antibiotics in poultry breeding has led to the frequent occurrence of antibiotic residues in poultry products, affecting food safety and posing a threat to human health. Accurate and rapid detection of antibiotic drug content is therefore of great significance. In this study, a new metamaterial method based on terahertz (THz) spectroscopy for the detection of the quinolone antibacterial drug noroxin in low concentrations was developed and tested. First, a new metamaterial structure was designed using a computational electromagnetics simulation tool with experimental verification. Three-dimensional full-wave electromagnetic field simulations and measured transmission spectra for the metamaterials were observed. Second, the transmission spectra of photoresists with different thicknesses (0-40µm) on the metamaterials surface were simulated, and the transmission spectra of noroxin thin films of different concentrations on the metamaterial surface were measured. Finally, using a purchased standard sample of noroxin in ethanol (100µg/mL) as the mother liquor, test samples of different concentrations were prepared, and experiments and multivariate data analysis were carried out. The noroxin detection limit for the method presented in this paper was determined as 0.01µg/mL. Thus, the new metamaterial method based on terahertz spectroscopy designed in this study was shown to effectively detect low concentrations of noroxin, providing a theoretical and experimental basis for the rapid detection of quinolone antibiotic residues in food matrices.

Detection of several quinolone antibiotic residues in water based on Ag-TiO2 SERS strategy

Herein, a surface-enhanced Raman scattering (SERS) strategy based on semiconducting substrate was exploited for detection of several antibiotic residues both in ultrapure water system and in actual water system. The as-prepared Ag-TiO2 (Ag synchronously deposited and doped TiO2) nanoparticle SERS-active substrate can achieve high sensitive SERS detection for difloxacin hydrochloride, ciprofloxacin, enrofloxacin, danofloxacin and enoxacin (five widely used quinolone antibiotics) in actual water samples, and the detection limits are as low as 4.36 × 10−12, 7.08 × 10−11, 3.94 × 10−11, 3.16 × 10−11 and 3.15 × 10−10 mol/L, respectively. These detection limits are far below the maximum of residue limit (3.01 × 10−7 mol/L) stipulated by the European Union. And, the desirable quantitative relationships can be obtained in a wide concentration range. The recoveries of five antibiotic residues from spiked actual water samples are found to be more than 80.8% with the relative standard deviations between 2.1% and 4.7%. Even, the proposed SERS method can accurately distinguish every antibiotic species from a mixed antibiotic residue sample with multiple antibiotics. And, Ag-TiO2 nanoparticles can also serve as an efficient photocatalyst for photocatalytic degradation of these antibiotic residues, which provides a multi-functional platform for synchronous determination and degradation of antibiotic residues in real environment.

Determination of Quinolone Antibiotic Residues in Human Serum and Urine Using High-Performance Liquid Chromatography/Tandem Mass Spectrometry.

Quinolone antibiotic residues may pose potential threat to human health. A rapid and sensitive method was developed for the determination of quinolone residues in human serum and urine. After solid phase extraction (SPE) process, eight quinolone residues were analyzed by high-performance liquid chromatography/tandem mass spectrometry (HPLC-MS/MS) using ciprofloxacin-d8 as the internal standard. The relative standard deviation of intra-day and inter-day precision for the eight quinolones were less than 7.52% and the accuracies ranged from 95.8% to 103% in human serum, and from 94.1% to 104% in human urine. The extraction recoveries for the eight quinolones varied from 80.2% to 113% in human serum and 83.4% to 117% in human urine. The limit of detection for the eight quinolones was 0.50-1.00 ng/mL. Quinolone antibiotic residues in human serum and urine from 12 volunteers were successfully analyzed with the validated method. The SPE-HPLC-MS/MS method was useful for accurate determination of quinolone antibiotic residues in human body.

Improved sample treatment for the determination of 17 strong sorbed quinolone antibiotics from compost by ultra high performance liquid chromatography tandem mass spectrometry

The use of compost from sewage sludge for agricultural application is nowadays increasing, since composting is recognized as one of the most important recycling options for this material, being a source of nutrients for plants but also of contamination by persistent pollutants. In the present work, a multi-residue analytical method for the determination of 17 quinolone antibiotic residues in compost using multivariate optimization strategies and ultra high performance liquid chromatography–tandem mass spectrometry has been developed. It is based on the use of microwave-assisted extraction at drastic conditions with ACN:m-phosphoric acid (1% w/v) for 5min at 120°C, in order to achieve a quantitative extraction of the compounds (>76% of extraction recovery). Extracts were cleaned-up by salt-assisted liquid–liquid extraction (SALLE) with NaCl at pH 1.5 (with HClO4) and then using a dispersive sorbent (PSA). After LC separation, the MS conditions, in positive electrospray ionization mode (ESI), were individually optimized for each analyte to obtain maximum sensitivity in the selected reaction monitoring mode (SRM). The analytes were separated in less than 7min. Cincophen was used as surrogate standard. The limits of detection ranged from 0.2 to 0.5ngg−1, and the limits of the quantification from 0.5 to 1.5ngg−1, while intra- and inter-day variability (% RSD) was under 7% in all cases. A recovery assay was performed with spiked samples. Recoveries ranging from 95.3% to 106.2% were obtained. Cleanup procedure reduced significantly matrix effects, which constitutes an important achievement, considering the important drawbacks of matrix components in quality and validation parameters. This method was applied to several commercial compost samples. Only 6 of the studied antibiotics were not detected in any of the samples. The antibiotics with the highest concentrations were ciprofloxacin (836ngg−1), ofloxacin (719ngg−1), and enrofloxacin (674ngg−1), which were also the only ones found in all the analyzed samples. The results showed that this method could also be potentially adapted for the analysis of other strong sorbed basic pharmaceuticals in solid environmental matrices.

Determination of 13 Quinolone Antibiotic Residues in Swine Muscle by UPLC-MS/MS

A method was developed for the simultaneous determination of 13quinolone(QNs)antibiobtics in swine muscle by ultra performance liquid chromatography tandem mass spectrometry(UPLC-MS/MS).The analytes were extracted from the sample using Na2EDTA-Mcllvaine buffer solution and phosphate buffer with ultrasonic bath and purified by solid-phase extraction(SPE)cartridge.Sample was analyzed in electrospray positive ion and multiple reaction monitoring(MRM)mode.Satisfied recoveries(64.55%—117.62%) of all the drugs are demonstrated in 5.0,50.0and 100.0μg/kg spiked levels with the RSD for intra-day and inter-day of 13analytes less than 14.28%and 12.81%.Limit of detection(LOD)and limit of quantitation(LOQ)are 1.0μg/kg and 5.0μg/kg.The method is sim-ple,accurate,sensitive and suitable for the determination of 13quinolone(QNs)antibiobtics in swine muscle.

Determination of five quinolone antibiotic residues in foods by micellar electrokinetic capillary chromatography with quantum dot indirect laser-induced fluorescence

A new assay was developed for the determination of five quinolone antibiotic residues in foods, loxacin, enrofloxacin, ciprofloxacin, lomefloxacin, and norfloxacin, by micellar electrokinetic capillary chromatography with indirect laser-induced fluorescence, in which cadmium telluride quantum dots were used as a fluorescent background substance. Some factors that affected the peak height and the resolution were examined. The optimized running buffer was composed of 20 mM SDS, 7.2 mg/L quantum dots, and 10 mM borate at pH 8.8. The separation voltage was 20 kV. Under these conditions, five quinolone antibiotic residues were separated successfully within 8 min. The detection limits ranged from 0.003 to 0.008 mg/kg; the linear dynamic ranges were all 0.01 ∼ 10 mg/kg; and the average recoveries of the spiked samples were 81.4 ∼ 94.6 %. The assay can meet the requirement of maximum residue limits to these five quinolone antibiotics in the regulations of the European Union and Japan and has been applied for determining their residues in animal-derived food.

Screening of quinolone antibiotic residues in chicken meat and beef sold in the markets of Ankara, Turkey

This study aimed to find the effects of quinolone antibiotics in chicken and beef used in Ankara, Turkey. Total number of 127 chicken and 104 beef meat samples were collected randomly from local markets for analysis. Extraction and determination of quinolones were made by ELISA procedure. One hundred eighteen of 231 (51.1%) examined chicken meat and beef samples were found to contain quinolone antibiotic residue. Among the chicken meat and beef samples, 58 (45.7%) of chicken meat samples and 60 (57.7%) of beef meat samples were positive for quinolones, respectively. The mean levels (±SE) of quinolones were found to be 30.81 ± 0.45 µg/kg and 6.64 ± 1.11 µg/kg in chicken and beef samples, respectively. This study indicated that some chicken and beef meat sold in Ankara contains residues of quinolone antibiotics.

Analysis of sulfonamide and quinolone antibiotic residues in Korean milk using microbial assays and high performance liquid chromatography

A new protocol to analyse sulfonamides and quinolones from cows’ and goats’ milk was developed. Seven antibiotics, sulfamonomethoxine (SMM), sulfadimethoxine (SDM), sulfamethazine (SMZ), sulfamerazine (SMR), sulfaquinoxaline (SQX), enrofloxacin (ERF), and ciprofloxacin (CIP), were analysed by microbial assays and HPLC. In microbial assays, 21 of 269 samples were screened to have possible antibiotic residues. In HPLC analysis 4 samples were detected to contain SMR (3 samples) and CIP (1 sample). The concentration of SMR in the cows’ milk was 12.2 μg kg −1, which is higher than the LOQ (limit of quantification) and LOD (limit of detection). The levels of SMR and CIP in the other 3 samples were between their LOD and LOQ. Based on this study, we were able to establish an analytical protocol for accurate and robust detection of sulfonamide and quinolone-type antibiotics in milk using two assays.

Microbiological detection of 10 quinolone antibiotic residues and its application to artificially contaminated poultry samples

To assess if microbiological inhibition tests for detection of antibiotic residues are suitable for routine screening for quinolone residues, the limit of detection (LOD) of 10 different quinolones and fluoroquinolones was determined. Two media were tested, one at pH 6 and the other at pH 8, each seeded with one of the following test strains: Bacillus subtilis, Escherichia coli or Bacillus cereus. LODs of the 10 substances were highest on plates seeded with B. cereus, intended for selective detection of tetracycline residues. The pattern of zones on the other four plates differed for the targeted quinolones: flumequine and oxolinic acid were detected at lower concentrations at pH 6, while the LODs of ciprofloxacin, enrofloxacin, danofloxacin, marbofloxacin, sarafloxacin and norfloxacin were lower at pH 8. Nine of the 10 quinolones were detected more easily with E. coli, but the LOD of difloxacin was lower with B. subtilis. Finally, the three most sensitive media were selected and fluid from chicken meat, spiked with eight quinolones near maximum residue limits (MRL), analysed on each plate. The plate seeded with E. coli at pH 8 detected five of eight quinolones at levels of interest, but an additional E. coli plate at pH 6 was necessary for detection of flumequine in species other than poultry and fish. None of the plates detected oxolinic acid and difloxacin at MRLs in muscle tissue.

Determination of (fluoro)quinolone antibiotic residues in pig kidney using liquid chromatography–tandem mass spectrometry: I. Laboratory-validated method

A new LC–MS/MS method has been developed for the multiresidue determination of 11 (fluoro)quinolone antibiotics (FQs), including acidic and amphoteric species, around their maximum residue level (MRL) in pig kidney. The procedure involves a common sample preparation by solid-phase extraction on disposable extraction cartridges followed by a fast reversed-phase liquid chromatography–tandem mass spectrometry analysis. The method was validated according to the Commission Decision 2002/657/CE. The accuracy of the method was satisfactory with recoveries included in the interval 80–100%. The precision results showed mean repeatability and reproducibility coefficients of 7.4% and 11.8%, respectively. Limits of quantification much lower than the MRLs could be obtained.

Determination of (fluoro)quinolone antibiotic residues in pig kidney using liquid chromatography-tandem mass spectrometry: Part II: Intercomparison exercise

A recently in-house validated method for the liquid chromatography-tandem mass spectrometry (LC-MS/MS) determination of eleven (fluoro)quinolone antibiotics (FQs) in pig kidney has been fully validated through an intercomparison exercise. This ring trial involved eight European laboratories and was based on the Commission Decision 2002/657/CE for validation of method and on the IUPAC protocol for method–performances studies. The laboratories data were submitted to a one-way analysis of variance. Satisfactory results were obtained for each FQ with regards to within- and between-laboratory reproducibility and accuracy. The method was validated for the simultaneous qualitative and quantitative determination of the eleven FQs in pig kidney around their maximum residue limit (MRL) as defined in the European Council Regulation 2377/90/EEC.